Journal of the American Chemical Society 2011-12-07

Nickel-catalyzed Suzuki-Miyaura reaction of aryl fluorides.

Mamoru Tobisu, Tian Xu, Toshiaki Shimasaki, Naoto Chatani

Index: J. Am. Chem. Soc. 48th ed., 133 , 19505-19511, (2011)

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Abstract

Two protocols for the nickel-catalyzed cross-coupling of aryl fluorides with aryl boronic esters have been developed. The first employs metal fluoride cocatalysts, such as ZrF(4) and TiF(4), which enable Suzuki-Miyaura reactions of aryl fluorides bearing electron-withdrawing (ketones, esters, and CF(3)), aryl and alkenyl groups as well as those comprising fused aromatic rings, such as fluoronaphthalenes and fluoroquinolines. The second protocol employs aryl fluorides bearing ortho-directing groups, which facilitate the difficult C-F bond activation process via cyclometalation. N-heterocycles, such as pyridines, quinolines, pyrazoles, and oxazolines, can successfully promote cross-coupling with an array of organoboronic esters. A study into the substituent effects with respect to both coupling components has provided fundamental insights into the mechanism of the nickel-catalyzed cross-coupling of aryl fluorides.© 2011 American Chemical Society